Harnessing
the
luminescence
potential
of
Cu(I)
complexes
in
aqueous
media
is
typically
hindered
by
their
poor
photostability
and
altered
properties.
Here,
we
report
synthesis,
engineering
morphological
characterization
a
hydrophobic
homoleptic
copper(I)
complex
entrapped
into
silica
nanoparticles,
Cu-I@SiO2
(where
“Cu-I”
designates
[Cu(2,9-diiodo-1,10-phenanthroline)2]+),
as
promising
stabilisation
strategy
towards
water
compatible,
complex-based
luminescence.
The
polyether
chain-decorated
nano-objects
are
spherical
with
an
average
diameter
ca.
10.8±1.9
nm.
Upon
dispersion
clear,
solution-like
suspensions
were
obtained.
Significantly,
photo-luminesce
upon
excitation
(Φem
=
5.10-4)
through
Metal-to-Ligand
Charge-Transfer
transition
(MLCT)
embedded
complexes.
In
contrast,
corresponding
silica-free
molecular
dissolved
environment
revealed
fully
quenched
emission.
Finally,
use
luminescent
probes
reported,
first
assessing
electrochemiluminescent
probes,
second
monitoring
photoluminescence
from
presence
whole
blood.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(11), P. 6700 - 6902
Published: May 15, 2024
1,10-Phenanthroline
(phen)
is
one
of
the
most
popular
ligands
ever
used
in
coordination
chemistry
due
to
its
strong
affinity
for
a
wide
range
metals
with
various
oxidation
states.
Its
polyaromatic
structure
provides
robustness
and
rigidity,
leading
intriguing
features
numerous
fields
(luminescent
scaffolds,
catalysis,
supramolecular
chemistry,
sensors,
theranostics,
etc.).
Importantly,
phen
offers
eight
distinct
positions
functional
groups
be
attached,
showcasing
remarkable
versatility
such
simple
ligand.
As
result,
has
become
landmark
molecule
chemists,
serving
as
must-use
ligand
versatile
platform
designing
polyfunctional
arrays.
The
extensive
use
substituted
phenanthroline
different
metal
ions
resulted
diverse
array
complexes
tailored
applications.
For
instance,
these
have
been
utilized
sensitizers
dye-sensitized
solar
cells,
luminescent
probes
modified
antibodies
biomaterials,
creation
elegant
architectures
like
rotaxanes
catenanes,
exemplified
by
Sauvage's
Nobel
Prize-winning
work
2016.
In
summary,
found
applications
almost
every
facet
chemistry.
An
aspect
specific
reactivity
each
pair
carbon
atoms
([2,9],
[3,8],
[4,7],
[5,6]),
enabling
functionalization
Furthermore,
it
possible
differentiate
position
pairs,
resulting
non-symmetrical
systems
tremendous
versatility.
this
Review,
authors
aim
compile
categorize
existing
synthetic
strategies
stepwise
polyfunctionalization
positions.
This
comprehensive
toolbox
will
aid
chemists
virtually
any
survey
encompass
seminal
from
1950s
present
day.
scope
Review
limited
1,10-phenanthroline,
excluding
more
intracyclic
heteroatoms
or
fused
aromatic
cycles.
Overall,
primary
goal
highlight
both
old
recent
that
find
applicability
mentioned
By
doing
so,
hope
establish
first
reference
synthesis,
covering
all
on
backbone,
inspire
concerned
devise
new
not
yet
explored.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
63(3), P. 1692 - 1701
Published: Jan. 8, 2024
This
work
presents
a
series
of
Cu(I)
heteroleptic
1,10-phenanthroline
chromophores
featuring
enhanced
UVA
and
visible-light-harvesting
properties
manifested
through
vectorial
control
the
copper-to-phenanthroline
charge-transfer
transitions.
The
molecules
were
prepared
using
HETPHEN
strategy,
wherein
sterically
congested
2,9-dimesityl-1,10-phenanthrolne
(mesPhen)
ligand
was
paired
with
second
phenanthroline
incorporating
extended
π-systems
in
their
4,7-positions.
combination
electrochemistry,
static
time-resolved
electronic
spectroscopy,
77
K
photoluminescence
spectra,
time-dependent
density
functional
theory
calculations
corroborated
all
experimental
findings.
model
chromophore,
[Cu(mesPhen)(phen)]+
(1),
lacking
4,7-substitutions
preferentially
reduces
mesPhen
lowest
energy
metal-to-ligand
(MLCT)
excited
state.
remaining
cuprous
phenanthrolines
(2–4)
reduce
π-conjugated
ligands
low-lying
MLCT
absorption
cross
sections
2–4
(εMLCTmax
=
7430–9980
M–1
cm–1)
significantly
broadened
across
visible
regions
spectrum
compared
to
1
6494
cm–1).
excited-state
decay
mechanism
mirrored
those
long-lived
homoleptic
phenanthrolines,
yielding
three
distinguishable
time
constants
ultrafast
transient
experiments.
These
represent
pseudo-Jahn–Teller
distortion
(τ1),
singlet–triplet
intersystem
crossing
(τ2),
relaxed
lifetime
(τ3).
Effective
light-harvesting
from
Cu(I)-based
can
now
be
rationalized
within
strategy
while
achieving
directionality
respective
transitions,
valuable
for
integration
into
more
complex
donor–acceptor
architectures
longer-lived
photosensitizers.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(35), P. 14368 - 14376
Published: Aug. 24, 2023
A
key
challenge
to
the
effective
utilization
of
solar
energy
is
promote
efficient
photoinduced
charge
transfer,
specifically
avoiding
unproductive,
circuitous
electron-transfer
pathways
and
optimizing
kinetics
separation
recombination.
We
hypothesize
that
one
way
address
this
develop
a
fundamental
understanding
how
initiate
control
directional
particularly
for
earth-abundant
first-row
transition-metal
coordination
complexes,
which
typically
suffer
from
relatively
short
excited-state
lifetimes.
Here,
we
report
series
functionalized
heteroleptic
copper(I)bis(phenanthroline)
have
allowed
us
investigate
directionality
intramolecular
metal-to-ligand
transfer
(MLCT)
as
function
substituent
Hammett
parameter.
Ultrafast
transient
absorption
suggests
complicated
interplay
MLCT
localization
solvent
interaction
with
Cu(II)
center
state.
This
work
provides
set
design
principles
in
complexes
can
be
used
efficiently
connecting
molecular
modules
catalysts
or
electrodes
integration
into
systems
light-driven
catalysis.
Inorganic Chemistry,
Journal Year:
2023,
Volume and Issue:
62(41), P. 16759 - 16769
Published: Oct. 2, 2023
One
of
the
main
challenges
in
developing
effective
copper(I)
photosensitizers
is
their
short
excited-state
lifetimes,
usually
attributed
to
structural
distortion
upon
light
excitation.
We
have
previously
introduced
charge-transfer
chromophores
general
formula
Cu(N^N)(ArNacNac),
where
N^N
a
conjugated
diimine
ligand
and
ArNacNac
substituted
β-diketiminate
ligand.
These
were
promising
regarding
tunable
redox
potentials
intense
visible
absorption
but
ineffective
as
photosensitizers,
presumably
due
lifetimes.
Here,
we
introduce
sterically
crowded
analogues
these
heteroleptic
with
bulky
alkyl
substituents
on
and/or
Structural
analysis
was
combined
electrochemical
photophysical
characterization,
including
ultrafast
transient
(UFTA)
spectroscopy
investigate
effects
groups
lifetimes
complexes.
The
molecular
structures
determined
by
single-crystal
X-ray
diffraction
display
more
ground
state
are
into
phenanthroline
or
NacNac
ligand,
showing
smaller
τ4
values
steric
hindrance.
UFTA
measurements
carried
out
determine
dynamics.
Sterically
encumbered
Cu5
Cu6
15-20
times
longer
than
unsubstituted
complex
Cu1,
likely
indicating
that
incorporation
inhibits
pseudo-Jahn-Teller
(PJT)
flattening
excited
state.
This
work
suggests
properties
can
be
readily
modified
dynamics
strongly
responsive
modifications.
The Journal of Chemical Physics,
Journal Year:
2024,
Volume and Issue:
160(14)
Published: April 14, 2024
Solar
fuels
catalysis
is
a
promising
route
to
efficiently
harvesting,
storing,
and
utilizing
abundant
solar
energy.
To
achieve
this
promise,
however,
molecular
systems
must
be
designed
with
sustainable
components
that
can
balance
numerous
photophysical
chemical
processes.
end,
we
report
on
the
structural
characterization
of
series
Cu(I)-anthraquinone-based
electron
donor-acceptor
dyads.
The
dyads
utilized
heteroleptic
Cu(I)
bis-diimine
architecture
copper(I)
bis-phenanthroline
chromophore
donor
anthraquinone
acceptor.
We
characterized
structures
complexes
using
x-ray
crystallography
density
functional
theory
calculations
properties
via
resonance
Raman
optical
transient
absorption
spectroscopy.
spectroscopy
revealed
excitation
metal-to-ligand
charge-transfer
(MLCT)
transition
transfers
delocalized
ligand
orbital.
demonstrated
each
dyad
formed
oxidized
copper-reduced
charge-separated
state.
Unlike
most
where
increasingly
bulky
substituents
phenanthroline
ligands
lead
longer
MLCT
excited-state
lifetimes,
here,
observe
decrease
in
long-lived
state
lifetime
increasing
steric
bulk.
lifetimes
were
best
explained
context
electron-transfer
rather
than
energy
gap
law,
which
typical
for
excited
states,
despite
complete
conjugation
between
moieties.
Nanoscale,
Journal Year:
2024,
Volume and Issue:
16(31), P. 14813 - 14830
Published: Jan. 1, 2024
The
enhanced
selective
oxidation
of
benzyl
alcohol
to
benzaldehyde
under
visible
light
is
achieved
through
atomically
precise
control
the
coordination
structure
single
copper
atoms
on
graphitic
carbon
nitride.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(14), P. 1978 - 1989
Published: June 29, 2023
ConspectusThe
high
energy
barriers
associated
with
the
reaction
chemistry
of
inert
substrates
can
be
overcome
by
employing
redox-active
photocatalysts.
Research
in
this
area
has
grown
exponentially
over
past
decade,
as
transition
metal
photosensitizers
have
been
shown
to
mediate
challenging
organic
transformations.
Critical
for
advancement
photoredox
catalysis
is
discovery,
development,
and
study
complexes
based
on
earth-abundant
metals
that
replace
and/or
complement
established
noble-metal-based
photosensitizers.Recent
work
focused
3d
metals,
containing
these
most
likely
would
scalable.
Although
low
lying
spin
doublet
("spin
flip")
excited
states
chromium(III)
metal-to-ligand
charge
transfer
(MLCT)
copper(I)
relatively
long
lifetimes,
electronic
many
other
fall
dissociative
potential
surfaces,
owing
population
highly
energetic
σ-antibonding
orbitals.
Indeed,
we
investigators
singlet
triplet
robust
closed-shell
are
too
short-lived
at
room
temperature
engage
bimolecular
reactions
solutions.
In
principle,
problem
could
designing
constructing
strong
field
π-acceptor
ligands,
where
thermally
equilibrated
MLCT
or
intraligand
might
well
below
upper
surfaces
3d-3d
states.
Notably,
such
design
elements
exploited
very
recent
iron(II)
systems.
Another
approach,
one
actively
pursued,
construct
5d
vertical
excitation
5d-5d
ground
state
geometry
require
energies
far
above
minima
As
requirement
met
tungsten(0)
arylisocyanides,
focus
our
aimed
development
photosensitizers.In
following
Account,
review
homoleptic
arylisocyanides.
Originally
reported
group
45
years
ago,
W(CNAr)6
exceptionally
large
one-
two-photon
absorption
cross-sections.
One-
produces
long-lived
(hundreds
nanoseconds
microsecond)
yields.
These
states,
which
reductants
E°(W+/*W0)
=
-2.2
-3.0
V
vs
Fc[+/0],
photocatalysis
both
visible
near-infrared
(NIR)
light.
Here,
highlight
principles
led
three
generations
photosensitizers;
discuss
steps
mechanism
a
prototypal
W(CNAr)6-catalyzed
base-promoted
homolytic
aromatic
substitution
reaction.
Among
applications
bright
luminophores,
imaging
two-photon-initiated
polymerization
ones
plan
pursue.
European Journal of Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Aug. 20, 2024
Abstract
The
synthesis
as
well
the
structural,
optical
and
computational
characterization
of
seven
new
highly
hindered
homoleptic
copper(I)
phenanthroline
complexes
(namely
C1
–
C7
)
is
reported
along
with
comparison
benchmark
derivatives.
Despite
limited
steric
hindrance
in
direct
proximity
coordination
site,
X‐ray
structures
show
that
higher
derivatives
series
display
a
more
optimal
tetrahedral
geometry
minimal
D
2
symmetry
distortion.
A
novel
remote
control
geometry,
away
from
leads
to
favorable
arrangement
demonstrated
by
structural
data.
In
addition,
electrochemical
steady‐state
time‐resolved
photophysical
studies
are
presented
which
further
support
beneficial
effects
on
ground‐state
redox
excited‐state
properties
when
both
close
exploited.
Indeed,
an
increase
photoluminescence
quantum
yield
prolongation
excited
state
lifetime
observed
for
highly‐substituted
derivative
C6
compared
counterparts
account
reduced
flattening
distortions
imparted
additional
constraints.
Pharmaceuticals,
Journal Year:
2023,
Volume and Issue:
16(5), P. 766 - 766
Published: May 19, 2023
Metal
complexes
feature
a
wide
range
of
available
geometries,
diversified
lability,
controllable
hydrolytic
stability,
and
easily
rich
redox
activity.
These
characteristics,
combined
with
the
specific
properties
coordinated
organic
molecules,
result
in
many
different
mechanisms
biological
action,
making
each
myriads
classes
metal
coordination
compounds
unique.
This
focused
review
presents
systematized
results
studies
group
copper(I)
(pseudo)halide
aromatic
diimines
tris(aminomethyl)phosphines
general
formula
[CuX(NN)PR